Abstract Very accurate vibrational spectra of silicates are obtained from DFT calculations if the appropriate Hamiltonian is used. Theoretical considerations suggest that the Hartree–Fock component of ACM1 hybrid functionals should be 1/6 instead of 1/4 for this class of compounds. When applied to the PBE functional this removes the scaling error of the calculated vibrational frequencies. Calculations using this PBE(n = 6) functional in combination with optimized Gaussian basis sets result in very small remaining deviations between observed and calculated Raman shifts, with standard uncertainties of ≈3.5 cm−1, maximum deviations of ≈10 cm−1, and no significant systematic trends. This has been confirmed for a wide range of silicate structures, for which high-quality Raman spectra have been published: forsterite α-Mg2SiO4 (nesosilicate), γ-Y2Si2O7 (sorosilicate), K2Ca3Si3O10 (oligosilicate), K2Ca4Si8O21 (phyllosilicate), and α-quartz SiO2 (tectosilictae).